GB2065141A - Improved Vinyl or Vinylidene Chloride Resin Metal Coating Compositions; Method for their Production and Articles Coated Therewith - Google Patents

Abstract

Polymers of vinyl chloride and/or vinylidene chloride containing carboxyl or sulphonic acid groups can be formulated as stable, aqueous, colloidal dispersions by converting them to ionomers in a mixture of water-miscible base, water, organic water-miscible macromolecular compound, water-miscible organic solvent for the polymer, water- miscible organic co-solvent (non- solvent for the polymer) and then stripping to a total organic solvent content of 0.2 to 20% by volume.

Description

SPECIFICATION Improved Vinyl Resin Metal Coating Compositions Method for Their Production and Articles Coated Therewith This invention pertains to the preparation of stable, aqueous colloidal dispersions of carboxylic acid or sulfonic acid-containing vinyl resins and more particularly to the preparation of vinyl resin colloidal dispersions by mixing said resins with water, base, an organic solvent, an organic co-solvent and a macromolecular compound.

Solution polymerized vinyl halide resins have been widely used as an interior coating resin for the beer and beverage cans. They are FDA approved vehicles, provide good protection for the metallic substrates from corrosive effects of the contents, and excellent blush-resistance during pasteurization while contributing no undesirable taste properties. For these reasons, they are preferred over most of the other coating resins for this demanding application.

Because these vinyl halide resins are normally applied as a lacquer, a large amount of organic solvents is evolved during the application. Being ecologically undesirable and expensive, this technology has been replaced rapidly by other technologies where the solvent requirement can be reduced to a much lower level. The most prominent one is the waterborne coatings technology.

A waterborne coating may be formed from a water-soluble resins, a latex, or an emulsion. A water-soluble resin formulation is often too water sensitive to pass the required blush resistance test.

On the other hand, latices and emulsions produced by the conventional methods almost always contain one or a combination of surfactants to effect the dispersion as well as fragments from the initiator system used. These additives often become a source of either poor blush resistance or possibly bad taste properties, or both.

It is therefore an object of this invention to prepare water-borne colloidal dispersions of vinyl resins suited for various coating applications.

A method of preparing water colloidal dispersions of vinyl resins suitable for various coating applications has been found which comprises: (A) blending vinyl resins selected from the class consisting of vinyl chloride, vinylidene chloride or vinyl chloride/vinylidene chloride copolymers having carboxylic or sulfonic acid groups contained therein with: (a) water; (b) a water-miscible base; (c) an organic water-miscible macromolecular compound; (d) at least one water-miscible, organic solvent which has an affinity for said resins and boils below 160"C.; and (e) an organic and water-miscible co-solvent which is a poor solvent for said resins but is miscible with the organic solvent (d); and (f) optionally a water-immiscible organic diluent until a stable colloidal dispersion forms; and (B) stripping the colloidal dispersion thus formed until the total organic solvent content and diluent, (d), (e) and (f), of the final colloidal dispersion is 0.2 to 20% by volume.

It is preferred to prepare these colloidal dispersions by blending: (A) a normally solid vinyl resin containing carboxylic or sulfonic acid groups and having the following moieties copolymerized therein

wherein Ir) and n are percentages each having a value of 0-99%, t is a percentage having a value of 0-59%; p is a percentage having a value of 130%, when q=O; q is a percentage having a value of 130%, when p=O with the proviso that m+n+t is > 70 and that that m+n+t+p+q=100% that when m=O, n is at least 1 and that when n=O, m is at least 1;; wherein Xis a monovalent radical selected from the group consisting of-H and lower alkyls having 1-4 carbons; W is a monovalent radical selected from the group consisting of -H, lower akyls, aryl having 6 to about 9 carbons,

wherein a is an integer having values of 1-3,

-OR (wherein R is C1-C18 alkyl), -OH, -C-N(R1)2 (wherein R1 is a monovalent radical selected from the group consisting of-H, methyl or ethyl), and -CN;; Y is a monovalent radical selected from group consisting of-H, methyl,

wherein b is an integer having values of 0-4, and Z is a monovalent radical selected from the group consisting of

-SO3H and -C6H4-SO3H, with the proviso that Y and Z are never -COOH and -SO3H at the same time, (B) sufficient water-miscible base to neutralize 10% to 100% of said carboxylic or sulfonic acid groups, (C) 1 to 500 parts, per 100 parts by weight of vinyl resin, of a water-miscible normally liquid solvent for said vinyl resin having a boiling point below 1 600 C., selected from the group consisting of lower aliphatic ketones, esters or ethers having 3 to about 6 carbon atoms and cycloaliphatic ketones or ethers having 4 to 6 carbon atoms;; (D) 1 to 500 parts, per 100 parts by weight of vinyl resin, of a normally liquid co-solvent which is a poor solvent for the vinyl resin but is miscible with water and solvent (C), selected from the group consisting of: (1) glycol monoalkyl ethers having the formula: HO#CHR"CHR"'O#,R"" where each of R", R"' is H or CH3, r is an integer having values of 1 to 3 and R"" is an alkyl group having 1 to 6 carbon atoms, or phenyl, (2) aliphatic acidic ethers having the formula: R""'O#CH2#,COOH wherein R""' is an alkyl group having 1 to 4 carbon atoms, (3) amino esters having the formula:

(4) amino ketones having the formula::

(5) aliphatic alcohols having the formula R2OH, where R2 is alkyl having 1 to 5 carbons, (6) aliphatic carboxylic acids having the formula:

where R3 is H or alkyl having 1 to 4 carbons, (7) aliphatic amines having the formula:

where R4 and R6 are H or alkyl having 1 to 6 carbons and R6 is alkyl having 1 to 6 carbons with the proviso that the total number of carbons in the sum of R4+R5+R6#6, (8) aliphatic amino ethers having the formula: [R70(cH2iiiNH3-r where R7 is methyl or ethyl, and g has values of 1-4, (9) aliphatic dialkyl amides having the formula: : R8CON(R7)2 where R8 is H or alkyl having 1 to 5 carbons, (10) N-(Hydroxymethyl)acrylarnide and N-(hydroxymethyl)methacrylamide having the formula: CH 2=CR9CONHCH2OH where Rug is H or-CH3, (11) cycloaliphatic ether alcohols having the formula:

where R10 is alkylene having 1 to 3 carbons and v is an integer having values of 1 to 5, (12) hydroxy esters having the formula:

(13) hydroxy ketones having the formula::

(E) O to 49 parts by weight of a water-immiscible organic diluent per hundred parts by weight of organic solvent (D) selected from the group consisting of alkanes having about 5 to 20 carbon atoms and halogenated alkanes having 2 to 20 carbon atoms, cycloalkanes and halogenated cycloalkanes having 5 to 1 2 carbon atoms, aromatic hydrocarbons having 6 to 12 carbon atoms, aliphatic or cycioaliphatic ketones having 7 to 12 carbon atoms, alkaryl ketones having 7 to 12 carbon atoms, aliphatic and aromatic esters having 7 to 12 carbon atoms and olefins having 6 to 20 carbon atoms;; (F) a water-miscible, normally solid macromolecular organic compound selected from the group consisting of cellulose ethers, poly(alkylene oxides), homopolymers of vinyl alcohol, acrylic acid, methacrylic acid, N-vinyl pyrrolidone or acrylamide and copolymers of vinyl alcohol, acrylic acid, methacrylic acid, N-vinyl pyrrolidone, maleic acid or acrylamide containing at least one of the following lipophilic moieties copolymerized therein:

wherein Y and R are as indicated above; and (F) sufficient water to provide an aqueous colloidal dispersion having a total solids content of up to 60% by weight; and then stripping the colloidal dispersion until the total content of organic solvents (C) and (D) and diluent (E) is 0.2 to 20% by volume.

The vinyl resins useful in this invention in their broadest sense are copolymers of vinyl chloride.

vinylidene chloride or both copolymerized with a vinyl comonomer containing at least one carboxylic acid group, -COOH or sulfonic acid group, -SO3H. Exemplary resins include copolymers of vinyl chloride and acrylic or methacrylic acid, vinyl chloride and maleic acid, vinyl chloride and styrene sulfonic acid: copolymers of vinylidene chloride and acrylic or methacrylic acid, vinylidene chloride and maleic acid, vinylidene chloride and styrene sulfonic.

The vinyl resins also encompass three component copolymers containing for example the following monomers copolymerized therein: vinyl chloride/vinyl acetate/acrylic acid vinyl chloride/vinyl acetate/maleic acid vinyl chloride/vinyl acetate/crotonic acid vinyl chloride/vinyl acetate/5-norbornene-2,3-di-carboxylic acid, monobutyl ester vinyl chloride/vinyl acetate/fumaric acid vinyl chloride/methyl methacrylate!maleic acid vinyl chloride/acrylonitrile/maleic acid vinyl chloride/styrene/maleic acid vinyl chloride/vinyl stearate/maleic acid vinyl chloride/2-propenyl acetate/maleic acid vinyl chloride/hydroxypropylacrylate/maleic acid vinyl chloride/glycidyl methacrylate/maleic acid vinyl chloride/acrylamide/maleic acid vinyl chloride/vinyl alcohoi/maleic acid vinyl chloride/vinyl butyl ether/maleic acid vinyl chloride/ethyl acrylate/maleic acid vinyl chloride/ethylene/maleic acid vinyl chloride/ethylene/acrylic acid vinyl chloride/propylene/maleic acid vinyl chloride/styrene/acrylic acid vinyl chloride/vinyl acetate/styrene sulfonic acid vinyl chloride/vinyl acetate/vinyl sulfonic acid, and the like as well as other terpolymers in which vinylidene chloride is substituted for vinyl chloride in this list.

In addition four component quadripolymers can also be used wherein both vinyl chloride and vinylidene chloride are copolymerized with the other comonomers shown in the terpolymers in the preceding paragraph.

The amount of each monomer copolymerized in the vinyl resins is not narrowly critical.

The ethylenically unsaturated carboxylic acids enumerated above as well as the other comonomers are commercially available. The more common sulfonic acid containing monomers are also commercially available or can be synthesized by sulfonation of ethylenically unsaturated monomers ranging from aliphatic monomers, such as, ethylene to aromatic monomers, such as, styrene, with known sulfonation agents, such as, listed in "Unit Processes in Organic Synthesis" by P.

H. Groggins, McGraw-Hill Co., Inc., page 262 NYC (1947).

The invention is not limited to single copolymers and so various combinations of two or more of these vinyl resins can be emulsified as well.

Preferred vinyl chloride resins include vinyl chloride terpolymers having 60 to 91 weight % vinyl chloride, 10 to 25 weight % vinyl acetate and 1 to 15 weight % of maleic acid, fumaric acid or crotonic acid copolymerized therein. Such terpolymers may be obtained commercially or may be synthesized by a free radical initiated polymerization of vinyl chloride, vinyl acetate and maleic acid, or maleic anhydride, fumaric acid or crotonic acid.

The above-described vinyl chloride resins can also be blended with vinyl chloride/vinyl acetate terpolymers containing glycidyl or hydroxyalkyl acrylates or methacrylates having 2 or 3 carbons in the alkyl group to afford cross-linked coatings. One can also add thermosetting resins, such as, epoxy resins urea resins and melamine resins to obtain a higher degree of cross-linking. Preferred epoxy resins include liquid and solid diglycidyl ethers bisphenol A which are commercially available and described in "Epoxy Resins" by H. Lee and K. Neville, McGraw-Hill and Co., Inc. NYC 1957, incorporated herein by reference.

Preferred melamine resins are the hexamethoxymethylmelamine resins. Preferred urea resins are the methylated urea-formaldehyde resins. These are commercially available.

Blush or whitening of the coatings is determined subjectively, a test well known to those skilled in the art.

Wet adhesion is measured by cross-hatch adhesive failure determinations. These are made by immersing coated specimens in water at 750C for 45 minutes, scratching a cross on the coated substrates with a sharp pointed instrument, pressing sections of Scotch tape across the scratched portions and then ripping the Scotch tape away from the coated surface. Failures are indicated by the amount of coating which pulls away from the substrate.

Exemplary co-solvents are presented below.

Representative glycol monoalkyl (phenyl) ethers are monomethyl, ethyl, propyl, butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and phenyl glycol ether.

Representative aliphatic acidic ethers include ethoxyacetic acid, ct-methoxy-propionic acid.

dimethoxy acetic acid, and ethoxy propionic acid.

Representative amino esters include methyl /3-aminopropionate, ethyl aminoacetate and ethyl aminopropionate.

Representative amino ketones include aminoacetone and 2-aminobutanone.

Representative aliphatic alcohols include, methanol, ethanol, propanols, butanols and pentanols.

Representative aliphatic carboxylic acids include formic, acetic, propionic, and butyric.

Representative aliphatic amines include methylamine, dimethylamine, methyl-ethylamine, dimethylamine, triethylamine, n-butylamine and hexyamine.

Representative aliphatic amino ethers include y-methoxy-n-propylamine, y-ethoxy-n propyiamine, p-methoxy-isobutylamine, and /3-ethoxy-n-butylamine.

Representative aliphatic dialkyl amides include N,N-dimethylformamide, N,N-diethylformamide and N,N-dimethylacetamide.

Representative cycloaliphatic ether alcohols include glycidol and tetrahydrofurfuryl alcohol.

Representative hydroxy esters include methyl lactate, methyi-P-hydroxypropionate and ethyl hydroxypropionate.

Representative hydroxy ketones include 1 -hydroxy-2-propanone, 1 -hydroxy-3-butanone, 3 methyl-4-hydroxy-2-buta none, 1 -hydroxy-2-pentanone and 4-hydroxy-2-pentanone.

The order of addition of the components used to prepare these colloidal dispersions is not critical.

Thus for example one may first make a varnish of the vinyl resin with the solvent and co-solvent, and optionally a diluent followed by conversion to an ionomer with base and then emulsification with water. The water can be added to the varnish or vice versa. One may also make these colloidal dispersions from dry vinyl resin rather than a varnish thereof, by adding pulverized resin pellets to a mixture of solvent, co-solvent, base, water and optionally a diluent.

Alternatively, the resin may be fed in the molten state from a vent extruder or a thin film evaporator into a mixture of solvent, co-solvent, water-miscible organic macromoiecular compound, base, and water with vigorous stirring.

The degree of neutralization of the acid moieties in the vinyl resin components can as pointed out above vary over a wide range, i.e., from 10% to 100%. The optimum degree of neutralization depends upon the amount of acid moiety in the vinyl resin. Thus for example a vinyl resin containing a low amount of acid moiety, e.g., 2 or 3 weight % should be neutralized with base to a much greater extent than a vinyl resin containing a large amount of acid moieties. This is believed to be due to the higher polarity of the higher acid moiety containing vinyl resins.

No special equipment is needed to effect emulsification other than agitation or mixing equipment known to those skilled in the art.

While not wishing to be bound by any theoretical explanation, it is believed that the formulation of the colloidal dispersions of this invention is achieved without the necessity of employing surfactants by the use of a combination of: (A) an organic solvent which (i) is water-miscible, i.e., at least 1% and preferably 10% or more water is soluble in said solvent on a weight basis; (ii) has an affinity for the vinyl resin used, i.e., the solvent/resin interaction is greater than the resin/resin interaction; (iii) has a boiling point below 1 600C., (B) an organic co-solvent which: (i) is as water-miscible as the solvent in (A); and (ii) is a poor solvent for the vinyl resin used, i.e., the co-solvent/resin interaction is < the resin/resin interaction; (C) an optional water-immiscible organic diluent; (D) a vinyl resin containing an ionomerfunctionality copolymerized therein; and (E) a water-miscible organic macromolecular compound for providing greater stability and better viscosity control of the dispersion.

The above-described combination of solvent and co-solvent surprisingly lowers the interfacial tension between the vinyl resin and the aqueous phase while avoiding coagulation. This affords the formation of a colloidal dispersion where the droplets are stabilized by the ionic repulsion of the ionomer moiety and the surfactant-like property of the co-solvent. When this stage is reached it is no longer necessary to maintain the original levels of solvent, co-solvent and/or diluent and concentration of the colloidal dispersion can be effected to afford a higher solids content. In the application of these colloidal dispersions to a substrate to form a coating the co-solvent also can be removed from the system with the water leaving only the vinyl resin to constitute the coating.In the case of vinyl resins neutralized with a volatile base, the ionomer in the vinyl resin reverts to the original free acid moiety.

The presence of a water-miscible macromolecular compound ensures a greater storage stability as well as a correct viscosity - total solids relationship during spraying operations.

It is a unique feature of the dispersions described herein that all necessary ingredients for a satisfactory interior can coating may be introduced at the time of emulsification. The finished colloidal dispersion may be used as is, or stripped to higher total solids by vacuum distillation, or thinned down to lower total solids by adding back water. Coating formulations prepared in this manner will exhibit satisfactory flow, atomization, and wetting characteristics which are essential requirements in airless spray applications.

Additionally, due to the extremely fine particle sizes present in these dispersions, very thin continuous protective films can be laid on both metallic and non-metallic substrates. The resultant films are pin-hole free, blush resistant and adhere tenaciously to the substrates.

If so desired, the water soluble macromolecules can be partially or completely withheld during the emulsification and introduced after the solvent stripping. For the purpose of viscosity control, additional thickening agents can also be employed preferably after the emulsification. Suitabie thickening agents include such water-soluble resins as, hydrolyzed polyvinyl acetates or polyvinyl alcohol, water-soluble cellulose derivatives, e.g., hydroxyethyl cellulose, polyethylene glycols, acrylic or methacrylic acid polymers, poly(E-caprolactone), polyvinyl pyrrolidone, and poly(methylvinyl ether).

Other additives known to those skilled in the art can also be incorporated into the colloidal dispersions if desired. These include dyes, pigments, fillers, antioxidants, ultraviolet stabilizers, and heat stabilizers.

For the purposes of this invention the term "water-miscible base" is used in the broad sense of any proton acceptor which will neutralize the acid functionalities in the vinyl resin, i.e., -COOH or SO3H groups and whose solubility is at least 1 g. per 1000 cc of water. Exemplary bases which may be organic or inorganic, include alkali metal or alkaline earth hydroxides, such as, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide; ammonium hydroxide; organic amines including monoalkylamines, alkenediamines, alkanolamines, aromatic amines, cyclic amines, and alkaryl amines. For economic reasons and ready availability alkali metal, alkaline earth and ammonium hydroxides are preferred inorganic bases.In coating application it is preferred to use volatile bases which are fugitive and consequently reversible ionomers are formed. For example, ammonium hydroxide or lower molecular weight alkylamines form ionomers which afford coatings wherein the ionomer moieties revert to acid and from which the base, being fugitive, is removed. This enhances blush resistance and minimize color formation upon exposure of the final coating to the elements. Particularly preferred alkylamines include monomethyl amine, dimethyl amine, trimethyl amine and triethyl amine.

In general, preferred alkyl amines have the formula:

wherein each of Ra, Rb and Rc is H or a C1-C6 alkyl with the proviso that Ra+Rb+R < 6 carbons.

Preferred alkylene diamines have the formula: H2N(D)XNH2 where x=1 -8 and D is alkylene radical.

Preferred alkanolamines include mono-, di-, and tri-ethanolamine, N-methyl ethanolamine, N,Ndimethylethanolamine, N,N-diethyl ethanolamine, N-aminoethylethanolamine, and Nmethyldiethanolamine.

Preferred cyclic amines include morpholine, N-methyl morpholine, piperidine, pyrrolidine, piperazine, N-methyl piperazine, N-(2-hydroxyethyl)piperazine, N-aminoethyl piperazine, 2,5-dimethyl piperazine, and hexamethylene tetramine.

Preferred lower aliphatic ketone solvents include acetone, methyl ethyl ketone (MEK), diethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, acetyl acetone, and 1-methoxy-2-propanone.

Preferred lower aliphatic ester solvents include methyl formate, ethyl formate, methyl acetate, ethyl acetate, and isopropyl acetate.

Preferred lower aliphatic ether solvents include diethyl ether, ethyl propyl ether, and di-n-propyl ether.

Preferred cycloaliphatic ketones solvents include cyclobutanone, cyclopentanone, and cyclohexanone.

Preferred cycloaliphatic ether solvents include, dioxane, and tetrahydrofurane.

Depending on the particular vinyl halide resin used, it may be preferable to use mixtures of these solvents rather than a single solvent. For example, with a vinyl chloride/vinylacetate/maleic acid terpolymer the combination of acetone with another ketone, such as methyl ethyl ketone, will give dispersions superior to those formulated with acetone alone. It is also permissable to use a mixture of cosolvent instead of a single cosolvent.

Occasionally, it may be desirable to modify the solvent system with a minor amount of a waterimmiscible organic diluent for reasons of matching the solubility parameters between the solvent system and the resin(s) to be dispersed. This may be done without adversely affecting the quality of the finished dispersion as long as the solvent system as a whole retains an adequate degree of water miscibility. It is preferred, however, that the water-immiscible organic diluent or its azeotrope with water boils at a lower temperature than water to facilitate its removal during the vacuum distillation.

Exemplary water-immiscible organic diluents which are miscible with both the solvents and cosolvents include: alkanes having 5 to 20 carbon atoms and halogenated alkanes having about 2 to about 20 carbon atoms, such as, pentane, hexane, heptane, 1-chloropentane, 1 ,2-dichloroethane, trichloroethylene, tetrachloroethylene, and 1 2-dibromohexane; cycloalkanes and halogenated cycloalkanes having 5 to 12 carbon atoms, such as, cyclopentane, cyclohexane, cycloheptane, chlorocyclohexane; aromatic hydrocarbons having 6 to 12 carbon atoms, including both unsubstituted and alkyl or halogen substituted hydrocarbons, such as, benzene, toluene, xylenes, chlorobenzene, and o- chlorotoluene;; aliphatic ketones having 7 to 1 2 carbon atoms, such as, propylbutyi ketone, dibutyl ketone and butyihexyl ketone; cycloaliphatic ketones having 7 to 12 carbon atoms, such as, cyclohexyl ketone, and cycloheptyl ketone; alkaryl ketones having 7 to 1 2 carbon atoms, such as, acetophenone, and propiophenone; aliphatic and aromatic esters having 7 to 1 2 carbon atoms, such as, ethyl benzoate, hexyl benzoate, methyl hexanoate, propyl octanoate, and hexyl acetate; olefins having 6 to 20 carbon atoms, such as, hexene-1, octene-2, octene-1, and eicosene-1.

While these water-immiscible diluents can be used at a level of up to 49 parts per hundred parts by weight of organic solvent, it is preferred however to use a level of 1 to 25 parts per hundred parts by weight of organic solvent.

A particularly preferred method of preparing colloidal dispersions of the vinyl resins described above comprises: A. blending said resins with: (a) water; (b) a water-miscible base; (c) an organic water-miscibie macromolecular compound; (d) 1 to 500 parts per hundred parts by weight of resins of at least one water-miscible organic solvent which has an affinity for said resin and boils below 1600 C; (e) 1 to 500 parts per hundred parts by weight of resin of an organic water-miscible co-solvent which is a poor solvent for said resins but is miscible with the organic solvent (d) (f) O to 49 parts of water immiscible organic diluent per hundred parts by weight of organic solvent (d); until a stable colloidal dispersion forms; and (B) stripping the colloidal dispersion until the total content of organic solvents (d) and (e) and diluent (f) of the final colloidal dispersion is 0.2 to 20% by volume.

If the total organic solvent content falls below 0.2% by volume the coatings produced from such formulation may contain pin holes and other voids. If the total content of organic solvents and diluent goes above 20% by volume general ecology standards are violated.

While it is not absolutely essential, if desired, an organic coalescing aid may be added to the stripped colloidal dispersion.

Exemplary coalescing aids include: (1) glycols having 2 to 6 carbon atoms, such as, ethylene glycol, 1,2-propylene glycol, diethylene glycol, and triethylene glycol; and (2) glycerine.

When used the coalescing aids should be present in an amount up to 25 parts by weight per 100 parts by weight of water in the colloidal dispersion.

The colloidal dispersions of this invention are particularly adapted to coating cans although other substrates both metallic and non-metallic can also be coated with these dispersions for their improved utility in packaging and myriad other applications which will become apparent to those skilled in the art upon a reading of the specification.

Cupric sulfate test is a test commonly used for detecting the presence of pin holes in an interior can coating. Satisfactory coatings should reveal no visible defects in this test.

Interior can coatings are usually applied by airless spray, a technique well known to those skilled in the art. While most examples described in this invention are based on a 2-piece aluminum cans, this invention is equally useful to 2-piece cans constructed of other metals as well as to 3-piece cans.

These metallic cans are used widely for the packaging of beer, beverage, and food.

The invention is further described in the examples which follow. All parts and percentages are by weight unless otherwise specified. A laboratory airless can spray unit consisting of an emulsion reservoir, a pumping unit, a pressure gauge, a timer, a heating device, a nozzle assembly, and a rotary can mount was employed.

Example 1 Preparation of Ammonium Hydroxide lonomer Dispersion To a varnish composed of 211.9 g. of Bakelite VMCC vinyl resin (a terpolymer containing 81% vinyl chloride, 17% vinyl acetate and 1% maleic acid copolymerized therein), 105 g. of Bakelite VERR vinyl resin (a terpolymer containing 80% vinyl chloride,11 vinyl acetate, and 9% glycidyl methacrylate copolymerized therein), 408.8 g. of methyl ethyl ketone, and 68.1 g. of butyl Cellosolve (a trade mark of Union Carbide Corporation for the monobutyl ether of ethylene glycol), was added with vigorous stirring 1,423 g. of an aqueous solution containing 10.5 g. of a 58% ammonium hydroxide solution, 21 g. of Gelvatol-2060 polyvinyl alcohol) resin (a partially hydrolyzed poly(vinyl acetate) resin produced by Monsanto), 10.5 g. of Beetle-60 (a methylated urea-formaldehyde resin produced by American Cyanamid). An aqueous dispersion characterized by an intense Tyndall scattering effect was obtained. The latter is usually associated with the formation of microemulsions or colloidal dispersions as defined in "Microemulsions-Theory and Practice", Academic Press, p.7 (1977), edited by L. M.

Prince. After vacuum stripping, the finished dispersion possessed the following composition and physical properties: % by weight Total Solids 32 Butyl Cellosolve 3.5 Ammonium Hydroxide 1 (approx.) Water 63.5 Brookfield Viscosity 1200 centipoise pH 7.5 Surface Tension 42 dynes/cm Example 2 Example 1 was repeated with the exception that Bakelite VMCC vinyl resin was replaced with Bakelite VMCA vinyl resin (a terpolymer containing 78% vinyl chloride, 20% vinyl acetate and 2% maleic acid copolymerized therein) and Gelvatol-2060 polyvinyl alcohol) resin was replaced with Gelvatol-2030 (a partially hydrolyzed poly(vinyl acetate) resin of lower molecular weight).After vacuum stripping, the finished dispersion exhibited the following composition and physical properties: % by weight Total Solids 40 Butyl Cellosolve 3 Ammonium Hydroxide 1 (approx.) Water 56 Brookfield Viscosity 1,400 centipoise pH 7.0 Surface Tension 42 dynes/cm Example 3 To a varnish composed of 45 g. of Bakelite VMCH vinyl resin (a terpolymer containing 86.5% vinyl chloride, 12.5% vinyl acetate, and 1% maleic acid), 113.3 g. of methyl ethyl ketone, and 22.7 g. of butyl Cellosolve, was added with vigorous stirring 364 g. of an aqueous solution containing 3 g. of a 58% ammonium hydroxide solution, 6 g. of Gelvatol-2090 poly(vinyl alcohol) resin (a partially hydrolyzed polyvinyl acetate) resin produced by Monsanto), 3 9. of Cymel-301 melamineformaldehyde resin (hexamethoxymethylmelamine sold by American Cyanamid). A uniform dispersion was obtained, which was stripped under vacuum to yield the following product:: % by weight Total Solids 18 Butyl Cellosolve 5.7 Ammonium Hydroxide 1 (approx.) Water 75.3 Brvokfield Viscosity 1,040 centipoise pH 7.5 Surface Tension 39 dynes/cm Example 4 To a varnish composed of 90 g. of Bakelite VMCH vinyl resin, 102 g. of MEK, and 34 g. of t-butyl alcohol was added with vigorous stirring an aqueous solution containing 3 g. of ammonium hydroxide, 6 g. of Gelvatol-2090 polyvinyl alcohol) resin, 3 g. of Cymel-301 melamineformaldehyde resin and 357 g. of water.The resulting emulsion was concentrated under vacuum at 500C to yield a product of the following composition and characteristics: % by weight Total Solids 20 Ammonium Hydroxide 1 (approx.) Water 79 Brookfield Viscosity 2,500 centipoise pH 7.0 Surface Tension 62 dynes/cm Example 5 Example 4 was repeated with the exception that Bakelite VMCH vinyl resin was replaced with an equal amount of Bakelite VMCC vinyl resin. The finished dispersion had the following composition and properties: % by weight Total Solids 20 Ammonium Hydroxide 1 (approx.) Water 79 Brookfield Viscosity 2,000 centipoise pH 7.0 Surface Tension 63 dynes/cm Example 6 Example 4 was repeated with the exception that Bakelite VMCH vinyl resin was replaced with an equal amount of Bakelite VMCA vinyl resin. The finished dispersion had the following composition and properties: % by weight Total Solids 19 Ammonium Hydroxide 1 (approx.) Water 80 Brookfield Viscosity 2,000 centipoise pH 6.5 Surface Tension 63 dynes/cm Example 7 Example 1 was repeated with the exception that Beetle-60 ureaformaldehyde resin was replaced with an equal amount of Cymel-301 melamine-formaldehyde resin.The finished dispersion had the following composition and properties: % by weight Total Solids 34 Butyl Cellosolve 3.6 Ammonium Hydroxide 1 (approx.) Water 61.4 Brookfield Viscosity 1,600 centipoise pH 7.5 Surface Tension 41 dynes/cm Example 8 Example 1 was repeated with the exception that Beetle-60 urea-formaldehyde resin was replaced with 14.3 g. of Beetle-55 urea-formaldehyde resin (a partially methylated urea-formaldehyde resin produced by American Cyanamid Co.) and Gelvatol-2060 was replaced with 28.59 of Elvanol51-05-G (a partially hydrolyzed polyvinyl acetate) resin produced by DuPont).The finished dispersion had the following composition and properties: % by weight Total Solids 38 Butyl Cellosolve 3 Ammonium Hydroxide 1 (approx.) Water 58 Brookfield Viscosity 610 centipoise pH 7.0 Surface Tension 43 dynes/cm Example 9 Example 1 was repeated with the exception that Gelvatol-206 poly(vinyl alcohol) resin was replaced with Vinol-540 (a partially hydrolyzed poly(vinyl acetate) produced by Air Products and Chemicals Inc.). The finished dispersion had the following composition and properties: % by weight Total Solids 30 Butyl Cellosolve 4 Ammonium Hydroxide 1 (approx.) Water 65 Brookfield Viscosity 3,700 centipoise pH 7.6 Surface Tension 39 dynes/cm Example 10 To a varnish composed of 60 g. of VMCC and 30 g. of VERR vinyl resins, 81 g. of acetone, 27 g.

of isopropyl acetate, and 27 g. of butyl Cellosolve was added with vigorous stirring 404 g. of an aqueous solution containing 6 g. of Beetle-60 urea-formaldehyde resin, and 3 g. of ammonium hydroxide. A uniformly dispersed emulsion was obtained.

Example 11 Example 10 was repeated with the exception that isopropyl acetate was replaced with an equal amount of hexane. A uniformly dispersed emulsion was obtained.

Type of Cans - Cleaned -- only aluminum cans Appearance - Clear and Glossy Mottling - None CuSO4 Test - Passed Enamel Rater Test - Below 20 MA Blush Resistance - Satisfactory Wet Adhesion - Satisfactory Taste Test - Satisfactory Example 20 A dispersion prepared according to Example 3 was thinned down with water and Propasol Solvent-B to give the following formulation: % by weight Vinyl Resin 13.5 Gelvatol-2090 1.0 Cymel-301 0.5 Ammonium Hydroxide 1 (approx.) Butyl Cellosolve 3.9 Propasol Solvent-B 1.3 Water 88.8 Brookfield Viscosity 280 centipoise No. 4 Ford Cup Flow Time 30 sec.

pH 8.5 The above dispersion was sprayed at room temperature under a pressure of 85 psi for 1 80 microsec. to produce a dry coating weight of 1 70 mg./can. Baking was carried out at 1 750C for 2 min. The finished interior coating exhibited the following properties: Type of Cans - Alodine 404 (non-chrome) with Reynolds "A" bottom can configuration Appearance - Clear and Glossy Mottling - None CuSO4Test Passed Enamel Rater Test - Below 20 MA Blush Resistance - Satisfactory Wet Adhesion - Satisfactory Taste Test - Satisfactory Example 21 A dispersion prepared according to Example 14 was diluted with an aqueous solution containing isopropyl alcohol and Propasol Solvent-P to yield the following formulation: % by weight Vinyl Resin 25 Gelvatol-2060 1.4 Beetle-55 0.7 Ammonium Hydroxide 1 Isopropyl Alcohol 2 Propasol Solvent-P 2 Butyl Cellosolve 2 Water 65.9 Brookfield Viscosity 275 centipoise No. 4 Ford Cup Flow Time 31 sec.

The above dispersion was sprayed at 400C under a pressure of 95 psi for 100 micro-sec. to produce a dry coating weight of 183 mg./can. Baking was carried out at 1 750C for 2 min. The finished interior coating showed the following properties: Type of Cans - Same as used in Example 20 Appearance - Clear and Glossy Mottling - None CuSO4 Test - Passed Enamel Rater Test - Below 20 MA Blush Resistance - Satisfactory Wet Adhesion - Satisfactory Taste Test - Satisfactory Example 22 A dispersion prepared according to Example 1 but without the Beetle-60 urea formaldehyde resin was used four making the following heat-sealable laminated films: An 1/2 mil thick dry coating was applied on a 1 mil annealed aluminum foil by using a wirewound rod and followed by baking at 1 750C for 8 minutes. The coated aluminum foil was smooth and glossy. Heat seals were prepared using a Sentinel heat sealer with the hot bar set at 2350C, a clamping pressure of 50 psi, and a duration of 2 seconds. The seals were found to have a satisfactory peel strength of 2 Ibs./in. (ASTM-D-1 876-61 T). A control applied from MEK/toluene solution yielded a peel strength of 2.1 Ibs./in.

Example 23 To a varnish composed of 90 g. of Bakelite VMCC vinyl resin, 108 g of MEK, and 27, 2 g of t-butyl alcohol, was added with vigorous stirring 41 6.5 g of an aqueous solution containing 3 g of ammonium hydroxide, 3 g of Beetle-55,12 g of GAF's PVP/VA 1-335 resin (a copolymer of N-vinyl pyrrolidone (30%) and vinyl acetate (70%), and 386.5 g of water. An aqueous dispersion characterized by an intense Tyndall scattering effect was obtained.After vacuum stripping, the finished dispersion possessed the following composition and physical properties: % by weight Total Solids 26 Total organic solvents 0.2 (approx.) Ammonium Hydroxide 1 (approx.) Water 72.8 Brookfield Viscosity 26 centipoise pH 7.5 Example 24 Example 23 was repeated with the exception that GAF's PVP/VA 1-335 resin was replaced with GAF's PVP/VA 1-535 (a copolymer of N-vinyl pyrrolidone (50%) and vinyl acetate (50%).After vacuum stripping, the finished dispersion possessed the following composition and physical properties: % by weight Total solids 28 Total organic solvents 0.2 (approx.) Ammonium Hydroxide 1 (approx.) Water 70.8 Brookfield Viscosity 24 centipoise pH 7.5 Example 25 Example 23 was repeated with the exception that GAF's PVP/VA 1-335 resin was replaced with GAF's PVP/VA 1-735 (a copolymer of N-vinyl pyrrolidone (70%) and vinyl acetate (30%). After vacuum stripping, the finished dispersion possessed the following composition and physical properties: % by weight Total solids 26 Total organic solvents 0.2 (approx.) Ammonium Hydroxide 1 (approx.) Water 72.8 Brookfield Viscosity 32 centipoise pH 7.5 Example 26 To a varnish composed of 92.8 lug of Bakelite VMCC vinyl resin, 207.5 g of acetone, 46.6 g of toluene, and 69.3 g of n-butyl alcohol, was added with vigorous stirring an aqueous solution containing 4.64 g of Ge!vatol-4010 (a partially hydrolyzed PVOH resin produced by Monsanto) 4.2 g of ammonium hydroxide, and 404 g of water A fine dispersion was obtained.After stripping under vacuum, the finished dispersion possessed the following composition and physical properties: Example 12 Example 10 was repeated with the exception that isopropyl acetate was replaced with an equal amount of tetrahydrofurane. A uniformly dispersed emulsion was obtained.

Example 13 One-half the amount of isopropyl acetate employed in Example 10 was replaced with toluene. A uniformly dispersed emulsion was obtained.

Example 14 To a varnish composed of 90 g. of Bakelite VMCC vinyl resin, 108.8 g. of MEK and 27.2 g. of butyl Cellosolve was added with vigorous stirring 393 g. of an aqueous solution containing 5 g. of Gelvatol-2060 poly(vinyl alcohol) resin, 3 g. of Beetle-55 urea formaldehyde resin, 3 g. of ammonium hydroxide and 381 g. of water. The dilute dispersion was vacuum stripped at 550C to yield the following product: % by weight Total Solids 35 Butyl Cellosolve 4 Ammonium Hydroxide 1 (approx.) Water 60 Brookfield Viscosity 1,100 centipoise pH 7 Surface Tension - 39 dynes/cm Example 15 Example 14 was repeated with the exception that an equal amount of Cymel-301 was used to substitute for the Beetle-55.After vacuum stripping, the finished dispersion possessed the following composition and characteristics: % by weight Total Solids 32 Butyl Cellosolve 4 Ammonium Hydroxide 1 (approx.) Water 63 Brookfield Viscosity 980 centipoise pH 7.5 Surface Tension 39 dynes/cm Example 16 To a varnish consisting of 90 g. of a (vinyl chloride-vinyl acetate-maleic acid) terpolymer, having the following composition and characteristics: % by weight Vinyl Chloride 64.5 Vinyl Acetate 23 Maleic Acid 12.5 Reduced Viscosity 0.18 (measured in cyclohexanone at 250C) 108.8 g. of methyl acetate and 27.2 g. of butyl Cellosolve was added with vigorous stirring 393 g. of an aqueous solution identical to the one employed in Example 14.The dilute dispersion was concentrated under vacuum to yield the following product: % by weight Total Solids 35 Butyl Cellosolve 3.5 Ammonium Hydroxide 1 (approx.) Water 61.5 Brookfield Viscosity 1,400 centipoise pH 6.5 Surface Tension 41 dynes/cm Example 17 Example 1 6 was repeated with the exception that the 3 g. of ammonium hydroxide was replaced with 6 g. of N,N-dimethyl ethanol amine. After solvent stripping, the finished emulsion possessed the following composition and characteristics: % by weight Total Solids 35 Butyl Cellosolve 3.5 N,N-Dimethyl Ethanolamine 2 Water 59.5 Brookfield Viscosity 1,600 centipoise pH 7.5 Surface Tension 39 dynes/cm Example 18 The waterborne coating formulations prepared in the above examples may be modified by a variety of additives commonly used in the coatings industry.For instance, the dispersion prepared n Example 1 may be modified with additional organic solvents for achieving better wetting, rheologic l, and filming properties. Some examples are listed in Table I. All formulations in Table I contained 20% by weight of total solids. Dilution was carried out by mixing the original dispersion with an aqueous solution containing the appropriate solvent or solvents.

Table Characteristics of Solvent-Modified Vinyl lonomeric Colloidal Dispersions Brookfield No. 4 Ford Cup ,Sesidual Solvent Type'1 Surface Tension Viscosity Flow Time {%byweíghtin VolatilePhaseJ dynes/cm cps sec.

BC(3.4) 44 67 13.8 By(3.4); POH(8.4) 34 51 14.0 BC(4.4); nBOH(3.7) 30 35 11.6 BC(3.4); PSB(0.9) 41 74 14.2 By(3,4): nHC(0.8); EOH(7.5) 31 26 12.2 BC(3.4); PSB(2.1); POH(6.3) 31 26 12.4 SC(3.4); PSP(2.1); POH(6.3) 34 48 13.6 BC(4.4); PG(1.6)r3, 43 275 42 (1) Where BC=Butyl Cellosolve; EOH=Ethanol; POH=Propyl Alcohol; nBOH=n-Butyl Alcohol; PSB=Propasol Solvent-B, a Union Carbide trade name for the monobutyl ether of propylene glycol: nHC=n-Hexyl Cellosolve; PSP=propasol solvent-P, a monopropylether of propylene glycol; PG=propylene glyol.

(2) A viscometer, the longer the flow time the greater the viscosity.

(3) Contained 24% total solids.

Example 19 Emulsions prepared in the above examples were evaluated as interior can coatings 9or some typical 2-piece aluminum cans. Coatings were applied with an airless spray unit consisting of a paint reservoir, a pump unit, a pre-heater, a spray-time controller, a nozzle assembly, and a rotary can mount.

The sprayed can was baked in an air-drift oven to cure the coating.

A dispersion prepared according to Example 1 was diluted with water and butyl Cellosolve to yield the following formulation: % by weight Vinyl Resins 25 Gelvatol-2060 1.67 Beetle-60 0.83 Ammonium Hydroxide 1 (approx.) Butyl Cellosolve 3.6 Water 67.9 1009/0 Brookfield Viscosity 216 centipoise No.4 Ford Cup Flow Time 25 sec.

pH 8.5 The above dispersion was sprayed at room temperature under a pressure of 90 psi for 1 50 micro sec. to produce a dry coating weight of 187 mg/can. Baking was carried out at 1756C for 2 min. The finished interior coating exhibited the following properties: % by weight Total solids 25 Total organic solvents 0.2 (approx.) Ammonium Hydroxide 0.8 (approx.) Water 74 Brookfield viscosity 46 centipoise pH 7 Example 27 To a varnish composed of 60 g of Bakelite VMCC vinyl resin, 30 g of VERR vinyl resin, 102 g of MEK, and 34 g of t-butyl alcohol, was added with vigorous stining 31 6 g of aqueous solution containing 4 g of Gelvatol-4010, 3 g of Beetle-60 and 3 g of ammonium hydroxide. A fine dispersion was obtained.After stripping under vacuum, the finished dispersion possessed the following composition and physical properties: % by weight Total solids 30 Total organic solvents 0.2 (approx.) Ammonium Hydroxide 0.8 (approx.) Water 69 Brookfield Viscosity 55 centipoise pH 7.5 Surface Tension 68 dynes/cm Example 28 Example 27 was repeated with the exception that only 90 g of VMCC vinyl resin was used, and Beetle-60 in the aqueous phase was replaced with the same amount of Cymel-301. A translucent dispersion was obtained. After stripping under vacuum, the finished dispersion had a total solids content of 38.4% by weight.

Example 29 A 200 gm quantity of the stripped dispersion prepared in Example 28 was mixed in a Waring blender with 5.1 g of Gelvatol-2090 PVOH resin, 12.3 g of n-butyl alcohol, 12.3 g of Propasol Solvent B, and 109 g of water. The diluted dispersion possessed the following composition and physical properties: % by weight Total solids 24 Total organic solvents 7.2 Ammonium Hydroxide 0.8 (approx.) Water 68 Brookfield viscosity 248 centipoise pH 7 Surface Tension 32.7 dynes/cm No. 4 Ford Cup Flow Time 48.8 sec.

Example 30 To a varnish composed of 87.1 g of VMCA vinyl resin, 98 g MEK and 32.7 g of Ethyl Cellosolve was added with vigorous stirring 269.7 g of an aqueous solution containing 1 g of Ceilosize-QP-40 (a hydroxyethyl cellulose resin produced by Union Carbide), 2 g of Cumel-301 and 8.7 g of trimethylamine (25% aqueous solution). A uniform dispersion was obtained. After vacuum stripping at 500C a dispersion containing 36.7% of total solids was obtained. It possessed a pH of 6.75 and a Brookfield viscosity of 656 centipoise.

Example 31 Example 30 was repeated with the exception that VMCA vinyl resin was replaced with 60 g of VMCC and 30 g VERR vinyl resins, and Cellosize-QP-40 was replaced with 1 g of Cellosize-QP-1 5,000.

A uniform dispersion was obtained. After vacuum stripping at 500C a dispersion containing 32.4% total solids was obtained. It possessed a pH of 7.8 and a Brookfield viscosity of 756 centipoise.

Example 32 Example 30 was repeated with the exception that the aqueous solution was replaced with another aqueous solution containing 24 g of Carbowax 200 (a poly(ethyleneglycol) resin produced by Union Carbide) 5 g of Beetle-60, 2.7 g of ammonium hydroxide and 258 g of water. A uniform dispersion was obtained. After solvent stripping, the finished product possessed a total solids content of 38%, a pH of 6.95, and a Brookfield viscosity of 38 centipoise.

Example 33 Example 32 was repeated with the exception that Carbowax 200 was replaced with Carbowax 6,000. A fine dispersion was achieved. After vacuum stripping, the finished product possessed a total solids of 33,6%, a pH of 7.2 and a Brookfield viscosity of 176 centipoise.

Example 34 Example 26 was repeated with the exception that no Gelvatol-4010 was used in the aqueous during the emulsification. A fine dispersion was obtained, which was vacuum distilled to a total solids of 35%.

One hundred grams of the above concentrated dispersion was mixed in a Waring blender with 2.45 g ofGelvatol-4010, 37.6 g of water, and two drops of ammonium hydroxide to yield a uniform formulation. The latter had a total solids of 25%, a pH of 7.8, and a Brookfield viscosity of 75 centipoise.

Example 35 A dispersion prepared according to Example 14 was modified with an aqueous solution containing Gelvatol-2090, Beetle-55, Butyl Cellosolve, and Propylene glycol to yield the following formulation: % by weight Vinyl Resin 20 Gelvatol-2060 and -2090 1.8 Beetle-55 0.9 Butyl Cellosolve 4.8 Propylene Glycol 1.6 Ammonium Hydroxide 0.8 (approx.) Water 70.1 Brookfield Viscosity 285 centipoise No. 4 Ford Cup Flow Time 32 sec.

The above dispersion was sprayed at 400C under a pressure of 95 asi for 120 micro-seconds to produce a dry coating weight of 165 mg/can. Baking was carried out at 175 C for 2 minutes. the finished interior coating showed the following properties: Type of cans - Same as used in Example 20 Appearance - Clear and glossy Mottling - None C4SO4Test Passed Enamel Rater Test - Below 20 MA Blush Resistance - Satisfactory Wet Adhesion - Satisfactory Taste Test - Satisfactory

Claims (30)

Claims

1. Method of preparing water-borne colloidal dispersions of one or more vinyl resins selected from the group consisting of vinyl chloride, vinylidene chloride or vinyl chloride/vinylidene chloride copolymers having carboxylic or sulfonic acid groups contained therein which comprises: A. blending said resin or resins with (a) a water-miscible base; (b) water; (c) an organic water-miscible macromolecular compound; (d) at least one water-miscible organic solvent which has an affinity for said resins and boils below 1 600C; and (e) an organic and water-miscible co-solvent which is a poor solvent for said resins but is miscible with the organic solvent (d); and (f) O to 49 parts by weight of a water-immiscible organic diluent per hundred parts by weight of organic solvent (d) until a colloidal dispersion forms; and B. stripping of the colloidal dispersion until the total content of organic soluents (d) and (e) and diluent (f) of +he final colloidal dispersion is 0.2 to 20% by volume.

2. Method of preparing water-borne colloidal dispersions of vinyl resins which comprises bending: (A) a normally solid vinyl resin containing carboxylic or sulfonic acid groups and having the following moieties copolymerized herein

wherein m and n are percentages each having a value of 0-99%; t is a percentage having a value of 0-59%; p is a percentage having a value of 1-30%, when q=O; q is a percentage having a value of 1-30%, when p=O with the proviso that m+n+t is #70 and < 99%, that m+n+t+p+q=100%, that when m=O, n is at least 1 and that when n=O, m is at least 1; wherein X is a monovalent radical selected from the group consisting of -H and lower alkyls having 1-4 carbons; W is a monovalent radical selected from the group consisting of -H, lower alkyls, aryl having 6 to 9 carbons,

wherein a is an integer having values of 1-3,

-OR (wherein R is a C1-C18 alkyl), -OH,

(wherein R, is a monovalent radical selected from the group consisting of -H, methyl or ethyl), and -CN; Y is a monovalent radical selected from the group consisting of-H, methyl;

wherein b is an integer having values of 0-4; and Z is a monovalent radical selected from the group consisting of

-SO3H and -C8H4-SO3H, with the proviso that Y and Z are neverCOOH and -SO3H at the same time, (B) sufficient water-miscible base to neutralize 10% to 100% of said carboxylic or sulfonic acid groups, (C) 1 to 500 parts, per 100 parts by weight of vinyl resin of a water-miscible normally liquid solvent for said vinyl resin having a boiling point of up to 1600 C., selected from the group consisting of lower aliphatic ketones, esters or ethers having 3 to 6 carbon atoms and cycloaliphatic ketones or ethers having 4 to 6 carbon atoms;; (D) 1 to 500 parts, per 100 parts by weight of vinyl resin, of a normally liquid co-solvent which is a poor solvent for the vinyl resin but is miscible with water and solvent (C), selected from the group consisting of: (1) glycol monoalkyl ethers having the formula: HO+CHR"CHRt"O+R't" where each of R", R"' is H or CH3, r is an integer having values of 1 to 3 and R"" is an alkyl group having 1 to 4 carbon atoms, (2) aliphatic acidic ethers having the formula: R""'O+CH24jCOOH wherein R""' is an alkyl group having 1 to 4 carbon atoms, (3) amino esters having the formula:

(4) amino ketones having the formula:

(5) aliphatic alcohols having the formula:R2OH where R2 is alkyl having 1 to 5 carbons, (6) aliphatic carboxylic acids having the formula:

where R3 is H or alkyl having 1 to 4 carbons, (7) aliphatic amines having the formula:

where R4 and R5 are H or alkyl having 1 to 6 carbons and R6 is alkyl having 1 to 6 carbons with the proviso that the total number of carbons in the sum of R4+R5+R8 < 6, (8) aliphatic amino ethers having the formula: [R,O+CH2*%NH3~, where Rz is methyl or ethyl, and g has values of 1-4, (9) aliphatic dialkyl amides having the formula: R8CoN(R7)2 where R8 is H or alkyl having 1 to 5 carbons, (10) N-(Hydroxymethyl)acrylamide and N-(hydroxymethyl)methacrylamide having the formula:: CH2=CR9CONHCH2OH where R9 is H or-CH3, (11) cycloaliphatic ether alcohols having the formula:

where R10 is alkylene having 1 to 3 carbons and v is an integer having values of 1 to 5, (12) hydroxy esters having the formula:

(13) hydroxy ketones having the formula:

(E) a water-miscible, normally solid macromolecular organic compound selected from the group consisting of cellulose ethers, poly(alkylene oxides), homopolymers of vinyl alcohol, acrylic acid, methacrylic acid, vinyl pyrrolidone or acrylamide and copolymers of vinyl alcohol, acrylic acid, methacrylic acid, vinyl pyrrolidone, maleic acid or acrylamide containing at least one of the following lipophilic moieties copolymerized therein::

wherein Y and R are as indicated above; and (F) O to 49 parts by weight of water immiscible organic diluent per 100 parts of organic solvent (D) selected from the group consisting of: (1) alkanes having 5 to 20 carbon atoms and halogenated alkanes having 2 to 20 carbon atoms; (2) cycloalkanes and halogenated cycloalkanes having 5 to 12 carbon atoms; (3) aromatic hydrocarbons having 6 to 1 2 carbon atoms; (4) aliphatic or cycloaliphatic ketones having 7 to 12 carbon atoms; (5) alkaryl ketones having 7 to 12 carbon atoms; (6) aliphatic or aromatic esters 7 to 12 carbon atoms; and (7) olefins having 6 to 20 carbon atoms; (G) sufficient water to provide an aqueous colloidal dispersion having a total solids content of up to 60% by weight; and then stripping the colloidal dispersion until the total content of organic solvents (C) and (D) and diluent (F) is 0.2 to 20% by volume.

3. Method claimed in claim 1 or 2, wherein the vinyl resin comprises a terpolymer which contains 60 to 91 weight % vinyl chloride, 10 to 25 weight % vinyl acetate and 1 to 15% carboxyl containing ethylenically unsaturated hydrocarbon.

4. Method claimed in claim 3, wherein the carboxyl-containing ethylenically unsaturated hydrocarbon is maleic acid orfumaric acid.

5. Method claimed in claim 1,2 or 3, wherein a mixture of a vinyl chloride/vinyl acetate/maleic acid terpolymer and a vinyl chloride/vinyl acetate/glycidyl acrylate or methacrylate terpolymer is used.

6. Method claimed in claim 1,2 or 3, wherein a mixture of a vinyl chloride/vinyl acetate/maleic acid terpolymer and a vinyl chloride/vinyl acetate/hydroxyalkyl acrylate or methacrylate having 2 to 3 carbons in the alkyl group is used.

7. Method claimed in claim 1, 2 or 3, wherein a mixture of a vinyl chloride/vinyl acetate/maleic acid terpolymer and a vinyl chloride/vinyl acetate/vinyl alcohol terpolymer is used.

8. Method claimed in claim 1 or 2, wherein the vinyl resin is a terpolymer of vinyl chloride, vinylidene chloride and an ethyienically unsaturated carboxylic acid.

9. Method claimed in claim 8, wherein the ethylenically unsaturated carboxylic acid is maleic acid orfumaric acid.

10. Method claimed in claim 8, wherein the ethylenically unsaturated carboxylic acid is acrylic or methacrylic acid.

11. Method claimed in claim 1 or 2, wherein the vinyl resin is a copolymer of vinyl chloride and an ethylenically unsaturated carboxylic acid.

12. Method claimed in claim 1 or 2, wherein the ethylenically unsaturated carboxylic acid is acrylic or methacrylic acid.

13. Method claimed in claim 12, wherein the vinyl resin contains 75 to 99 weight % vinyl chloride 1 to 25% acrylic or methacrylic acid copolymerized therein.

14. Method claimed in claim 1 or 2, wherein the vinyl resin is a copolymer of vinylidene chloride and an ethylenically unsaturated carboxylic acid.

1 5. Method claimed in any of claims 1 to 14, wherein a cross-linking amount of a thermosetting resin is blended into the colloidal dispersion.

1 6. Method claimed in claim 15, wherein the thermosetting resin is an epoxy resin, a hexamethoxy methyl melamine or a methylated urea-formaldehyde resin.

1 7. Method as claimed in any of claims 1 to 16, wherein organic solvent (D) is acetone or methyl ethyl ketone, the organic co-solvent (E) is butyl Cellosolve or a butanol, and the water immiscible organic diluent (F) is toluene or a hexane.

1 8. Method as claimed in any of claims 1 to 17, wherein the organic water-miscible macromolecular compound is a homopolymer or copolymer of vinyl alcohol.

19. Method as claimed in claim 18, wherein the copolymer contains the moiety:

wherein R is as defined above.

20. Method claimed in any of claims 1 to 19, wherein the organic water-miscible macromolecular compound is a homopolymer or copolymer of N-vinyl pyrrolidone.

21. Method claimed in claim 20, wherein the copolymer contains the moiety:

wherein R is as defined above.

22. Method claimed in any of claims 1 to 21, wherein the resin is blended with 1 to 25 parts by weight of a water-immiscible organic diluent per 100 parts by weight of organic solvent (d).

23. Method as claimed in claim 22, wherein the water-immiscible organic diluent is n-hexane, toluene or dibutyl ketone.

24. Method as claimed in any of claims 1 to 23, wherein up to 25 parts by weight of a coalescing aid, selected from the class consisting of glycols having 2 to 6 carbon atoms and glycerine, per 100 parts by weight of water added to the stripped colloidal dispersion.

25. A modification of the method claimed in any of claims 1 to 24, wherein either a part or all of the macromolecular organic compound (E) is added after stripping the colloidal dispersion.

26. A water-borne colloidal dispersion obtained by the method claimed in any of claims 1 to 25.

27. An article comprising a substrate and adhering to said substrate a film deposited from a water-borne colloidal dispersion claimed in claim 26.

28. A method as claimed in any of claims 1 to 25, substantially as hereinbefore described in any of the Examples.

29. A water-borne colloidal dispersion as claimed in claim 26, substantially as hereinbefore described in any of the Examples.

30. An article as claimed in claim 27, substantially as hereinbefore described in any one of Examples 19, 20, 21,22 and 35.